CN102241819A - Preparation method of thioxanthone-modified polyethyleneimine photoinitiator - Google Patents
Preparation method of thioxanthone-modified polyethyleneimine photoinitiator Download PDFInfo
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Abstract
The invention discloses a preparation method of a thioxanthone-modified polyethyleneimine photoinitiator shown a formula (I). The preparation method comprises the following step of: reacting epoxy propoxy thioxanthone with polyethyleneimine in a solvent to obtain a product. The photoinitiator prepared by the preparation method disclosed in the invention can be used for initiating polymerization reaction to prepare a star-shaped acrylamide polymer shown in a formula (II), wherein a core A is the thioxanthone-modified polyethyleneimine shown in the formula (I); and an arm B is an acrylamide homopolymer or a copolymer formed by acrylamide and a copolymerization monomer, the molar ratio of the copolymerization monomer to acrylamide is 0.3-0.6%, and the copolymerization monomer is selected from one of sodium p-styrene sulfonate, sodium 2-acrylamido-2-methyl propane sulfonate and octadecyl dimethyl propenyl ammonium chloride.
Description
Technical field
The present invention relates to a kind of preparation method of thioxanthone modified polyethyleneimine light trigger.
Background technology
The method for preparing at present star polymer has atom transfer radical polymerization, reversible addition-fracture chain transfer polymerization and ring-opening polymerization etc. usually, but these method reaction conditionss require harsh, the polymkeric substance that makes also is generally the star polymer of oil soluble, narrow molecular weight distribution, small molecular weight, and is not suitable for preparing good water solubility, polymkeric substance that molecular weight is big.Light-initiated radical polymerization also can be used to prepare star polymer, and this method reaction conditions gentleness only needs multi-functional light trigger just can make star polymer under suitable condition.Among the patent CN1594369 polypropylene has been obtained the dendroid thioxanthone photo initiator after imine modified, utilize light-initiated radical polymerization to be combined in the mixed solvent of water and dimethyl sulfoxide (DMSO) and prepared tree nuclear star type polyacrylamide, but because the dendroid thioxanthone photo initiator after the modification is water-soluble relatively poor, and be reflected in the mixed solvent and carry out, its molecular weight of product is less.Raw materials used polypropylene imines does not have industrial goods at present in the initiator simultaneously, and the cost height is unfavorable for industrial production.In order to obtain the light trigger that high-molecular weight star polyacrylamide is necessary to research and develop water-soluble good, polyfunctional group, wide material sources.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of thioxanthone modified polyethyleneimine.
The preparation method of thioxanthone modified polyethyleneimine shown in the formula provided by the invention (I) comprises the steps: that 2-glycidoxy thioxanthone and polymine react promptly to get product in solvent;
Polymerization degree N=1-16 wherein.
In the above-mentioned method, described polymerization degree N can be 1-6,3-6,1,3,6 or 16.
In the above-mentioned method, the polymerization degree of described polymine can be 1-16, and weight-average molecular weight Mw can be 600g/mol-10000g/mol; The ratio of quality and the number of copies of described 2-glycidoxy thioxanthone and described polymine can be 5: 2.
In the above-mentioned method, the polymerization degree of described polymine can be 1-6,3-6,1,3,6 or 16.
In the above-mentioned method, described solvent can be chloroform, thionyl chloride, N, dinethylformamide or dithiocarbonic anhydride.
In the above-mentioned method, the time of described reaction can be 16 hours-36 hours; The temperature of described reaction can be 40 ℃-70 ℃.
The thioxanthone modified polyethyleneimine light trigger that the invention provides the method preparation can be used for the star-like polyacrylamide base polymer of polymine shown in the initiated polymerization preparation formula (II) for nuclear.
Wherein, nuclear A is thioxanthone modified polyethyleneimine shown in the formula (I), wherein polymerization degree N=1-16; Arm B is methacrylamide homopolymer or the multipolymer that formed by acrylamide and comonomer.
In the above-mentioned polymkeric substance, the mol ratio of described comonomer and described acrylamide can be 0.3%-0.6%, specifically can be 0.3%-0.35%, 0.35%-0.4%, 0.4%-0.5% or 0.5%-0.6%.
In the above-mentioned polymkeric substance, when arm B is methacrylamide homopolymer, described polymine can be 3800000g/mol-4200000g/mol for the weight-average molecular weight Mw of the star-like polyacrylamide base polymer of nuclear, number-average molecular weight Mn can be 1800000g/mol-2900000g/mol, and branching factor g can be 0.49-0.77.
In the above-mentioned polymkeric substance, when arm B was the multipolymer that is formed by acrylamide and comonomer, described polymine can be 16dL/g-21dL/g for the intrinsic viscosity of the star-like polyacrylamide base polymer of nuclear.
In the above-mentioned polymkeric substance, described comonomer is selected from Sodium styrene sulfonate, 2-acrylamido-2-methyl propane sulfonic acid sodium and the octadecyl dimethyl allene ammonium chloride any.
Can confirm that the polymine for preparing is the branched structure of the star-like polyacrylamide homopolymer of nuclear in order to following method: adopt branching factor g to describe the degree of branching of star-like polyacrylamide homopolymer (star-like PAM), it is defined as: when molecular weight is identical, and all square rotation radius R of branched polymer chain
G, LAll square rotation radius R with the linear macromolecule chain
G, SThe ratio.G＜1, and the g value reduces with number of branches purpose increase in the molecule.Provided all square rotation radius R of linear polypropylene acid amides homopolymer and star-like polyacrylamide homopolymer among Fig. 3
gRelational expression with molecular weight Mw.As shown in Figure 3, along with the increase of polymine (PEI) molecular weight, the branching factor of corresponding star-like PAM reduces thereupon, simultaneous verification the branched structure of star-like PAM.
Above-mentioned polymine is the star-like polyacrylamide base polymer of nuclear, when arm B is methacrylamide homopolymer, described polymine for the weight-average molecular weight Mw of star-like polyacrylamide base polymer of nuclear for specifically can be 3800000-4200000g/mol, 3980000-4140000g/mol, 3800000g/mol, 3980000g/mol, 4080000g/mol, 4130000g/mol, 4140000g/mol or 4200000g/mol; Number-average molecular weight Mn specifically can be 1800000-2900000g/mol, 1800000-2310000g/mol, 1800000g/mol, 1840000g/mol, 1970000g/mol, 2310000g/mol, 2870000g/mol or 2900000g/mol; Branching factor g specifically can be 0.49-0.70,0.55-0.70,0.49,0.55 or 0.77.
Above-mentioned polymine is the star-like polyacrylamide base polymer of nuclear, and when arm B was the multipolymer that is formed by acrylamide and comonomer, its intrinsic viscosity specifically can be 16-17dL/g or 17-21dL/g.
Utilize polymine shown in the thioxanthone modified polyethyleneimine light trigger catalyzed polymerization formula (II) that method provided by the invention prepares for the method for the star-like polyacrylamide base polymer of nuclear comprise the steps: under the illumination with the acrylamide triggered aqueous solution of thioxanthone modified polyethyleneimine shown in the described formula (II) or, the mixed aqueous solution polyreaction of acrylamide and described comonomer obtains the star-like polyacrylamide base polymer of polymine shown in the described formula (I) for nuclear; The mol ratio of described comonomer and acrylamide is 0.3%-0.6%.
Among the above-mentioned preparation method, described comonomer is selected from sodium p styrene sulfonate, 2-acrylamido-2-methyl propane sulfonic acid sodium and octadecyl dimethyl allene ammonium chloride.
Among the above-mentioned preparation method, the concentration of aqueous solution of thioxanthone modified polyethyleneimine can be 10-30 * 10 shown in the described formula (II)
-6Mol/L; The massfraction of the aqueous solution of described acrylamide can be 25%-30%, and preferred 30%; The massfraction of described acrylamide and the monomeric mixed aqueous solution of copolymerization can be 25%-30%, and preferred 30%.
Among the above-mentioned preparation method, described polyreaction can be carried out in the silica glass groove.
Among the above-mentioned preparation method, the light source of described polyreaction can be the high voltage mercury lamp of 100W-1000W, preferred 500W high voltage mercury lamp.
Among the above-mentioned preparation method, described silica glass groove is placed on the top of the described high voltage mercury lamp 10cm-15cm of distance.
Among the above-mentioned preparation method, the mol ratio of described comonomer and acrylamide specifically can be 0.3%-0.35%, 0.35%-0.4%, 0.4%-0.5% or 0.5%-0.6%.
Among the above-mentioned preparation method, the temperature of described polyreaction can be 10 ℃-45 ℃, preferred 30 ℃; The time of described polyreaction can be 30min-70min, specifically can be 30min or 40min.
The end capped polymine light trigger of a kind of water-soluble thioxanthone of method preparation of the present invention, this initiator has dendritic structure, has higher light-initiated performance, for having bigger realistic meaning by light-initiated aqueous solution polymerization prepared in reaction practicality three-dimensional polymer.
Description of drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of TX-PEI600, TX-PEI800, TX-PEI3000 and TX-PEI10000.
Fig. 2 is the infrared spectrum of TX-PEI600, TX-PEI800, TX-PEI3000 and TX-PEI10000.
Fig. 3 is all square rotation radius R of linear polypropylene acid amides homopolymer and star-like polyacrylamide homopolymer
gRelation curve with molecular weight Mw.M at known star-like PAM
wAfter, bring the R of LPAM into
gVs.M
wObtain the R of the LPAM under the corresponding molecular weight in the relational expression
g, by both R
gRatio can obtain the branching factor of this star-like PAM.
Fig. 4 is for PEI1800 being the GPC spectrogram of the PEI1800-PAM of nuclear.
Fig. 5 is the mensuration spectrogram of partial hydrolysis PEI1800-PAM intrinsic viscosity in 1mol/L NaCl.
Fig. 6 is the infrared spectrogram of partial hydrolysis PEI1800-PAM.
Fig. 7 is the nucleus magnetic hydrogen spectrum figure of partial hydrolysis PEI1800-PAM.
Fig. 8 is the mensuration spectrogram of PEI10000 for the star-like hydrophobically modified acrylamide/octadecyl dimethyl-allyl ammonium chloride copolymer intrinsic viscosity of nuclear.
Fig. 9 is the infrared spectrum of PEI10000 for the star-like hydrophobically modified acrylamide/octadecyl dimethyl-allyl ammonium chloride copolymer of nuclear
Figure 10 is the nucleus magnetic hydrogen spectrum figure of PEI10000 for the star-like hydrophobically modified acrylamide/octadecyl dimethyl-allyl ammonium chloride copolymer of nuclear.
Figure 11 is the viscosity-concentration relationship curve of star-like hydrophobically modified acrylamide/octadecyl dimethyl-allyl ammonium chloride copolymer.
Figure 12 is the viscosity-temperature dependency curve of star-like hydrophobically modified acrylamide/octadecyl dimethyl-allyl ammonium chloride copolymer.
Figure 13 is the star-like hydrophobically modified acrylamide/octadecyl dimethyl-allyl ammonium chloride copolymer of nuclear and the flow performance curve after line style acrylamide/octadecyl dimethyl-allyl ammonium chloride copolymer shearing for PEI10000.
Figure 14 is the star-like partially hydrolyzed polyacrylamide of nuclear and the flow performance curve of linear partially hydrolyzed polyacrylamide for PEI10000.
Figure 15 is the flow performance curve after partial hydrolysis PEI600-PAM and partial hydrolysis PEI1800-PAM shear.
Figure 16 is the flow performance curve of different concns SHMPAM-0.3 after shearing.
Figure 17 is the oil displacement experiment result of PEI10000 for the star-like hydrophobically modified acrylamide/octadecyl dimethyl-allyl ammonium chloride copolymer of nuclear.
Embodiment
Employed experimental technique is ordinary method if no special instructions among the following embodiment.
Used material, reagent etc. if no special instructions, all can obtain from commercial channels among the following embodiment.
The present invention adopts branching factor g to describe the degree of branching of star-like polyacrylamide homopolymer (star-like PAM), and it is defined as: when molecular weight is identical, and all square rotation radius R of branched polymer chain
G, LAll square rotation radius R with the linear macromolecule chain
G, SThe ratio.
The preparation of thioxanthone modified polyethyleneimine shown in embodiment 1, the formula (II)
(1) preparation of 2-glycidoxy thioxanthone
The 16g thiosalicylic acid is dissolved in the 150mL vitriol oil stirring at room 10min; Slowly drip 44g phenol, react 1h under the room temperature, be warmed up to 80 ℃ of reaction 2h down then, standing over night.Reaction solution is slowly poured in the 1500mL boiling water, finished and continue to boil 30min; Be cooled to filter about 60 ℃, obtain intermediate product 2-hydroxyl thioxanthone after the oven dry.13.68g 2-hydroxyl thioxanthone, 21g Anhydrous potassium carbonate, 100mL epoxy chloropropane are joined in the 120mL toluene, 80 ℃ are reacted 12h down, react 12h down at 135 ℃ then, react the cooled and filtered that finishes, be spin-dried for excessive epoxy chloropropane and solvent, residue utilizes chloroform extraction to obtain 80.5g 2-glycidoxy thioxanthone.
(2) preparation of thioxanthone modified polyethyleneimine
1g2-glycidoxy thioxanthone is dissolved in the chloroform of 10mL that (dissolving is not exclusively down for low temperature, can dissolve fully after the heating), add the 0.4g polymine, its weight-average molecular weight Mw is respectively: 600g/mol (N=1), 1800g/mol (N=3), 3000g/mol (N=6) or 10000g/mol (N=16) (ratio of quality and the number of copies of 2-glycidoxy thioxanthone and the reaction of corresponding polymine is 5: 2) are warming up to 60 ℃ of reaction 24h down.After reaction finishes solution poured into the sedimentation and filtration drying obtains the thioxanthone modified polyethyleneimine in the 100mL sherwood oil, be labeled as successively: thioxanthone end-blocking PEI600 (TX-PEI600), thioxanthone end-blocking PEI1800 (TX-PEI1800), thioxanthone end-blocking PEI3000 (TX-PEI3000) and thioxanthone end-blocking PEI10000 (TX-PEI0000).
The hydrogen nuclear magnetic resonance spectrogram of gained thioxanthone end-blocking PEI as shown in Figure 1, its spectral data is as follows: thioxanthone end-blocking PEI600 (TX-PEI600):
1H NMR (CDCl
3, 300MHz): δ 8.59-7.22 (phenyl ring), 4.14-4.00 (OCH
2), 3.67-2.67 (NH
2-CH
2, NH-CH
2, N-CH
2), 1.49-0.82 (CH
2); Thioxanthone end-blocking PEI1800 (TX-PEI1800):
1H NMR (CDCl
3, 300MHz): δ 8.46-7.20 (phenyl ring), 4.13-3.86 (OCH
2), 3.68-2.67 (NH
2-CH
2, NH-CH
2, N-CH
2), 1.26-0.82 (CH
2); Thioxanthone end-blocking PEI3000 (TX-PEI3000):
1H NMR (CDCl
3, 300MHz): δ 8.60-7.18 (phenyl ring), 4.33-3.85 (OCH
2), 3.70-2.65 (NH
2-CH
2, NH-CH
2, N-CH
2), 1.52-0.81 (CH
2); Thioxanthone end-blocking PEI10000 (TX-PEI0000):
1H NMR (CDCl
3, 300MHz): δ 8.30-6.91 (phenyl ring), 4.76-3.90 (OCH
2), 3.73-2.66 (NH
2-CH
2, NH-CH
2, N-CH
2), 1.49-0.82 (CH
2).
The infrared spectrum of gained thioxanthone end-blocking PEI as shown in Figure 2, its spectral data is as follows: thioxanthone end-blocking PEI600 (TX-PEI1600): FT-IR (KBr): 3353cm
-1(O-H, N-H), 2933cm
-1(C-H), 1632cm
-1(C=O); Thioxanthone end-blocking PEI1800 (TX-PEI1800): 3369cm
-1(O-H, N-H), 2936cm
-1(C-H), 1632cm
-1(C=O); Thioxanthone end-blocking PEI3000 (TX-PEI3000): 3362cm
-1(O-H, N-H), 2934cm
-1(C-H), 1632cm
-1(C=O); Thioxanthone end-blocking PEI10000 (TX-PEI0000): 3365cm
-1(O-H, N-H), 2935cm
-1(C-H), 1632cm
-1(C=O).
The results of elemental analyses of gained thioxanthone end-blocking PEI sees Table 1.
The ultimate analysis of the different thioxanthone end-blocking of table 1 PEI
The preparation of embodiment 2, star-like methacrylamide homopolymer
The preparation massfraction is 30% acrylamide solution 100mL (containing the 30g acrylamide), pour in the rectangle silica glass groove reaction solution into (150 * 90 * 40mm), add thioxanthone modified polyethyleneimine (TX-PEI1800) 0.0027g, the concentration of thioxanthone modified polyethyleneimine (TX-PEI1800) is 15 * 10
-6Mol/L, behind the letting nitrogen in and deoxidizing 30min glass guide channel is sealed the top that is placed on apart from 500W high voltage mercury lamp 15cm, this moment, ultraviolet ray was by shining reaction solution behind the filter plate ZJB360, react the block that 30min obtains star-like polyacrylamide homopolymer down at 30 ℃, shred, obtain the star-like polyacrylamide homopolymer (PEI1800-PAM) of thioxanthone modified polyethyleneimine after the dehydrated alcohol precipitation, drying for nuclear, reaction conversion ratio is 99.6%, and its GPC curve as shown in Figure 4.
Its weight-average molecular weight Mw is: 4130000g/mol, number-average molecular weight Mn is: 184000g/mol, branching factor g are 0.70.
In kind obtain PEI600-PAM, PEI3000-PAM and PEI10000-PAM, its weight-average molecular weight Mw is respectively: 3980000,414000 and 4080000g/mol, number-average molecular weight Mn is respectively: 2310000,1970000 and 2870000g/mol, and branching factor g is respectively 0.77,0.55 and 0.49.
The preparation of embodiment 3, the star-like polyacrylamide homopolymer of partial hydrolysis
The preparation massfraction is 25% acrylamide solution 100mL (containing the 25g acrylamide), pour in the rectangle silica glass groove reaction solution into (150 * 90 * 40mm), add thioxanthone modified polyethyleneimine (TX-PEI1800) 0.0018g, the concentration of thioxanthone modified polyethyleneimine (TX-PEI1800) is 10 * 10
-6Mol/L, behind the letting nitrogen in and deoxidizing 30min glass guide channel is sealed the top that is placed on apart from 500W high voltage mercury lamp 10cm, this moment, ultraviolet ray was by shining reaction solution behind the filter plate ZJB360, react the block that 30min obtains star-like polyacrylamide homopolymer down at 30 ℃, shred, add 10wt%NaOH solution 40-70mL, dehydrated alcohol precipitation behind 70-90 ℃ of hydrolysis 3h, obtain the partial hydrolysis star-like polyacrylamide homopolymer of thioxanthone modified polyethyleneimine after the drying for nuclear, the mensuration spectrogram of its intrinsic viscosity in 1mol/L NaCl as shown in Figure 5, infrared spectra and nucleus magnetic hydrogen spectrum are respectively as shown in Figure 6 and Figure 7.
Its intrinsic viscosity is 22.45dL/g, and viscosity-average molecular weight is 12390000g/mol.
In kind obtain partial hydrolysis PEI600-PAM, PEI3000-PAM and PEI10000-PAM, its intrinsic viscosity is respectively: 19.82dL/g, 21.45dL/g, 20.12dL/g, viscosity-average molecular weight is respectively: 10600000g/mol, 11700000g/mol, 10800000g/mol.
The preparation of embodiment 4, star-like hydrophobically modified acrylamide/octadecyl dimethyl-allyl ammonium chloride copolymer
The preparation massfraction is 30% solution 100mL, solute is that acrylamide and octadecyl dimethyl-allyl ammonium chloride (wherein contain 30g acrylamide and 0.49g octadecyl dimethyl-allyl ammonium chloride, wherein, the following document of synthetic reference of octadecyl dimethyl-allyl ammonium chloride: Xie Yu, Zhang Changhui, Xu Xuan. the synthetic and performance study of polymeric quaternary ammonium salts cats product. household chemicals science .2007.16-10), wherein the mol ratio of octadecyl dimethyl-allyl ammonium chloride and acrylamide is 0.35%, pour in the rectangle silica glass groove reaction solution into (150 * 90 * 40mm), add 0.0036g thioxanthone modified polyethyleneimine (TX-PEI10000), the concentration of thioxanthone group is 25 * 10
-6Mol/L, behind the letting nitrogen in and deoxidizing 30min glass guide channel is sealed the top that is placed on apart from 500W high voltage mercury lamp 15cm, this moment, ultraviolet ray was by shining reaction solution behind the filter plate ZJB360, react the block that 40min obtains star-like hydrophobically modified polyacrylamide down at 30 ℃, shred, add 10wt%NaOH solution 40-70mL, dehydrated alcohol precipitation behind 70-90 ℃ of hydrolysis 3h, obtain the star-like hydrophobically modified acrylamide/octadecyl dimethyl-allyl ammonium chloride copolymer (SHMPAM-0.35) of thioxanthone modified polyethyleneimine after the drying, the mensuration spectrogram of its intrinsic viscosity for nuclear, infrared spectrum and nucleus magnetic hydrogen spectrum figure are respectively as Fig. 8, Fig. 9 and shown in Figure 10.
Its intrinsic viscosity is 17.24dL/g.
The mol ratio that in kind obtains octadecyl dimethyl-allyl ammonium chloride and acrylamide is star-like acrylamide/octadecyl dimethyl-allyl ammonium chloride copolymer (being labeled as SHMPAM-0.3, SHMPAM-0.4, SHMPAM-0.5 and SHMPAM-0.6 respectively) of 0.3%, 0.4%, 0.5% and 0.6%, and its intrinsic viscosity is respectively: 20.40,17.10,16.97 and 16.06dL/g.
The anti-shear performance research of star-like hydrophobically modified acrylamide/octadecyl dimethyl-allyl ammonium chloride copolymer of embodiment 5, embodiment 4
Joining poly-water with SZ36-1 oil field, the Bohai Sea is solvent, and the practicality situation of star-like hydrophobically modified acrylamide/octadecyl dimethyl-allyl ammonium chloride copolymer of investigation embodiment 4 is as going into.Join that various ion content sees the following form 2 in the poly-water:
Table 2 is joined the polywater particle and is formed (mg/L)
With PEI10000 is nuclear, during different hydrophobic monomer content, 45 ℃ down the dissolution time of star-like hydrophobically modified acrylamide/octadecyl dimethyl-allyl ammonium chloride copolymers see Table 3.
The solvability of the star-like acrylamide of table 3 embodiment 4/octadecyl dimethyl-allyl ammonium chloride copolymer
With TX-PEI10000 is nuclear, and during different hydrophobic monomer content, the star-like hydrophobically modified acrylamide of the embodiment 4/sticking dense curve of octadecyl dimethyl-allyl ammonium chloride copolymer (SHMPAM) under 65 ℃ seen Figure 11.Wherein, the preparation method of line style acrylamide/octadecyl dimethyl-allyl ammonium chloride copolymer (LHMPAM-0.4) is as follows: the preparation massfraction is 30% solution 100mL, solute is acrylamide and octadecyl dimethyl-allyl ammonium chloride (wherein containing 30g acrylamide and 0.56g octadecyl dimethyl-allyl ammonium chloride), wherein the mol ratio of octadecyl dimethyl-allyl ammonium chloride and acrylamide is 0.40%, reaction solution is poured in the beaker of 250mL, add 0.009g water-soluble azo initiator V50, behind the letting nitrogen in and deoxidizing 30min beaker is sealed the baking oven internal reaction 4h that is placed under 40 ℃, obtain the block of line style hydrophobically modified polyacrylamide, shred, add 10wt%NaOH solution 40-70mL, dehydrated alcohol precipitation behind 70-90 ℃ of hydrolysis 3h, obtain line style hydrophobically modified acrylamide/octadecyl dimethyl-allyl ammonium chloride copolymer (LHMPAM-0.40) after the drying.
With TX-PEI10000 is nuclear, and during different hydrophobic monomer content, the star-like hydrophobically modified acrylamide of the embodiment 4/viscosity-temperature curve of octadecyl dimethyl-allyl ammonium chloride copolymer (SHMPAM) under 1750mg/L seen Figure 12.
With TX-PEI10000 is nuclear, during difference hydrophobic monomer content, 300mL copolymer solution (concentration is 1750mg/L) is poured in the glass jar of Waring agitator of 1L, and next shelves of room temperature are sheared 20s, 65 ℃ measure solution shear down before and after viscosity change as shown in table 4.
The anti-shear performance of star-like hydrophobically modified acrylamide/octadecyl dimethyl-allyl ammonium chloride copolymer of table 4 embodiment 4
The essential property of to sum up star-like hydrophobically modified acrylamide/octadecyl dimethyl-allyl ammonium chloride copolymer shows: during identical octadecyl dimethyl-allyl ammonium chloride content, the apparent viscosity of star-like hydrophobically modified acrylamide/octadecyl dimethyl-allyl ammonium chloride is than line style hydrophobically modified acrylamide/octadecyl dimethyl-allyl ammonium chloride copolymer height; The content of octadecyl dimethyl-allyl ammonium chloride is 0.3% o'clock, and star-like hydrophobically modified acrylamide/octadecyl dimethyl-allyl ammonium chloride copolymer just can satisfy annotates the poly-required basic demand of polymkeric substance of using.
The aging research of star-like hydrophobically modified acrylamide/octadecyl dimethyl-allyl ammonium chloride copolymer of embodiment 6, embodiment 4
The use of the variation direct impact polymer of polymer solution viscosity under formation condition.Oxidative degradation and biological degradation may take place in polymkeric substance in the stratum.Prepare the star-like hydrophobically modified acrylamide/octadecyl dimethyl-allyl ammonium chloride copolymer solution (SHMPAM-0.3) of the PEI10000 of different concns respectively for nuclear, logical nitrogen 1h, 65 ℃ are taken out sample test viscosity behind the placement different time down, the results are shown in Table 5.
As can be seen from Table 5, PEI10000 has good permanent stability for the star-like hydrophobically modified acrylamide/octadecyl dimethyl-allyl ammonium chloride copolymer solution of nuclear, and when strength of solution was 1750mg/L, the sticking rate of the guarantor after 90 days was 81.3%, viscosity is 72.8, meets index request substantially.
Table 5PEI10000 is star-like hydrophobically modified acrylamide/octadecyl dimethyl-allyl ammonium chloride copolymer (SHMPAM-0.3) the solution long-term thermal stability of nuclear
The mobility control capability study of the star-type polymer of embodiment 7, embodiment 2-embodiment 4 preparations
1, experimental article and condition
The multi-functional physical chemistry drive apparatus of laboratory apparatus: HQY (Hai'an, Chinese Jiangsu); The displacement pump: the ISCO high-pressure pump, can carry out constant speed, constant voltage control, minimum flow rate 0.00001mL/min.
The circular homogeneous synthetic core of one dimension, wherein 1#-4# rock core cross-sectional area 10.75cm are used in experiment
2, length 29cm, the gas-phase permeation rate is about 3000mD, porosity about 30% (rock core water phase permeability and porosity are as the criterion with the experiment actual measurement), 5#-8# rock core cross-sectional area is 18.78cm
2, length 30.18cm, concrete rock core character sees Table 6 (LHPAM is linear partially hydrolyzed polyacrylamide in the table).Rate of displacement and requirement: initial water drive speed: 5m/d, polymer flooding and follow-up water drive speed 5m/d.
Experimental temperature: 65 ℃.
2, experimental result
The concrete outcome of experiment is seen Figure 13 to 16 and table 7 (LHPAM is linear partially hydrolyzed polyacrylamide in the table).As shown in Table 7, when polymkeric substance does not contain hydrophobic monomer, all (both molecular weight ratio are more approaching greatly than linear polyacrylamide LPAM for the resistance coefficient of star partial hydrolysis PEI1800-PAM and residual resistance factor, the solution apparent viscosity is about 15mPas), this may be because the molecular conformation of partial hydrolysis PEI1800-PAM more shrinks, enter less capillary pore easilier, therefore can enter more capillary pore, poly-to cause core permeability to descend when driving bigger, so resistance coefficient is bigger.When changeing water drive more afterwards, owing in the more hole partial hydrolysis PEI1800-PAM is arranged all, the partial hydrolysis PEI1800-PAM that is trapped in the capillary pore is also more, so residual resistance factor also can be bigger.
When polymkeric substance contains hydrophobic monomer, PEI10000 for the injection efficiency of star-like hydrophobically modified acrylamide/octadecyl dimethyl-allyl ammonium chloride copolymer SHMPAM-0.3 of nuclear significantly better than LHMPAM (seeing Figure 13), though the resistance coefficient of SHMPAM-0.3 is lower than LHMPAM, the former residual resistance factor is but than the height of LHMPAM.This result may be because the conformation of SHMPAM-0.3 is shunk relatively equally, after when entering hole, experiencing rock core shear fracture molecular interaction, the easier porous medium that enters of SHMPAM-0.3, so injection efficiency is better relatively, can enter more hole simultaneously.The viscosity ratio LHMPAM of SHMPAM after entering in the porous medium is low, so resistance coefficient is lower.During follow-up water drive, may be equally because to be trapped in the partial hydrolysis PEI1000-PAM of capillary pore more, so residual resistance factor big (seeing Figure 14).
During the difference degree of branching, the resistance coefficient of polymkeric substance increases with the increase of the apparent viscosity of solution, but the residual resistance factor of polymkeric substance increases (see Table 7 and Figure 15) with the increase of polymeric degree of branching, may also be because the high polymkeric substance of the degree of branching more shrinks and can enter more hole.
As shown in figure 16, the working concentration that changes SHMPAM-0.3 can find that when polymer solution concentration is respectively 1200mg/L and 1500mg/L resistance coefficient and residual resistance factor are respectively 15.3 (4.9) and 19.1 (6.4).
The essential property of table 6 rock core
Resistance coefficient and residual resistance factor after the different shearings of table 7
The displacement of reservoir oil performance study of the star-type polymer of embodiment 8, embodiment 4 preparations
1, experimental article and condition
The multi-functional physical chemistry drive apparatus of laboratory apparatus: HQY (Hai'an, Chinese Jiangsu); The displacement pump: the ISCO high-pressure pump, can carry out constant speed, constant voltage control, minimum flow rate 0.00001mL/min.
Two dimensional cross-section vertical heterogeneity synthetic core, cross-sectional area 19.86cm are used in experiment
2, length 29.17cm, each layer gas-phase permeation rate is respectively about 500mD, 1500mD and 4000mD from top to bottom, porosity about 30% (rock core water phase permeability and porosity are as the criterion with the experiment actual measurement).Concrete rock core character sees Table 8.
With comprehensive oil sample dehydration back, SZ36-1 oil field, the Bohai Sea and the composite simulated oil of kerosene, 65 ℃ of viscosity are 70mPas.
Output liquid is instantaneous during rock core metaideophone polymkeric substance moisturely requires 98%.
Rate of displacement and requirement: polymkeric substance and water drive speed: 3m/d.Polymers soln injects volume 0.3PV.
Experimental temperature: 65 ℃; Polymers soln: SHMPAM-0.3 is used in experiment, 1750mg/L, and sheared 20 seconds for one grade with Waring Blender 300mL solution preparation back.
The table 8 oil displacement experiment essential property of rock core
2, experimental result
SHMPAM-0.3 oil displacement experiment result as shown in figure 17, water drive is to 2.03PV, the instantaneous water content of extraction liquid is stable to be reached more than 98%, injection pressure stabilizes to 0.030MPa, the crude oil recovery percent of reserves is 30.98%; The poly-0.3PV of metaideophone afterwards, injection pressure increases rapidly, the highest 0.15MPa that increases to, the instantaneous water content of extraction liquid descends, and minimumly drops to 80.5%, and the crude oil recovery percent of reserves rises simultaneously; After annotating coalescent bundle, follow-up water drive begins, and injection pressure begins to descend, and the instantaneous water content of extraction liquid slowly rises, and the different crude oils recovery percent of reserves is still rising, and after follow-up water drive finished, the crude oil recovery percent of reserves was 46.15%, compares with previous water drive and has improved 15.17%.
Claims (6)
1. the preparation method of thioxanthone modified polyethyleneimine shown in the formula (I) comprises the steps: that 2-glycidoxy thioxanthone and polymine react promptly to get product in solvent;
Polymerization degree N=1-16 wherein.
2. method according to claim 1 is characterized in that: described polymerization degree N is 1-6,3-6,1,3,6 or 16.
3. method according to claim 1 and 2 is characterized in that: the polymerization degree of described polymine is 1-16, and weight-average molecular weight Mw is 600g/mol-10000g/mol; The ratio of quality and the number of copies of described 2-glycidoxy thioxanthone and described polymine is 5: 2.
4. according to arbitrary described method among the claim 1-3, it is characterized in that: the polymerization degree of described polymine is 1-6,3-6,1,3,6 or 16.
5. according to arbitrary described method among the claim 1-4, it is characterized in that: described solvent is chloroform, thionyl chloride, N, dinethylformamide or dithiocarbonic anhydride.
6. according to arbitrary described method among the claim 1-5, it is characterized in that: the time of described reaction is 16 hours-36 hours; The temperature of described reaction is 40 ℃-70 ℃.
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| US20120046377A1 (en) * | 2009-04-30 | 2012-02-23 | Siegwerk Benelux Sa | Photoinitiators |
| CN104497220A (en) * | 2015-01-04 | 2015-04-08 | 西南石油大学 | Starlike anti-shearing polyacrylamide for fracturing fluid and preparation method of starlike anti-shearing polyacrylamide |
| CN104558630A (en) * | 2015-01-04 | 2015-04-29 | 西南石油大学 | Water-soluble photoinitiator of thioxanthone-modified dendritic polyamide-amine and synthesis method |
| CN106933029A (en) * | 2015-12-31 | 2017-07-07 | 大东树脂化学股份有限公司 | Alkali-soluble smooth initiator copolymer of novelty tool as well as preparation method and application thereof |
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| CN106543355B (en) * | 2016-07-13 | 2020-07-10 | 成都菲尔特技术开发有限公司 | Hydrophobic association polymer and preparation method thereof |
| CN109266322B (en) * | 2018-09-10 | 2020-04-14 | 四川大学 | High-toughness polyacrylamide gel oil displacement agent and preparation method thereof |
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| CN1594369A (en) * | 2004-07-01 | 2005-03-16 | 上海交通大学 | Branch-shape macromolecular type thioxanthone photoinitiator and preparation method thereof |
| CN101665575A (en) * | 2009-10-15 | 2010-03-10 | 上海交通大学 | Amphiphilic hyper-branched thioxanthone photoinitiator and preparation method thereof |
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| CN1472233A (en) * | 2003-06-05 | 2004-02-04 | 上海交通大学 | Water soluble high molecular thioanthrone light initiator and its preparation |
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| CN101665575A (en) * | 2009-10-15 | 2010-03-10 | 上海交通大学 | Amphiphilic hyper-branched thioxanthone photoinitiator and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《Polymer》 20040131 Xuesong Jiang et al Polymeric w amine bearing side-chain thioxanthone as a novel photoinitiator 133-140 1-6 第45卷, * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20120046377A1 (en) * | 2009-04-30 | 2012-02-23 | Siegwerk Benelux Sa | Photoinitiators |
| US8598249B2 (en) * | 2009-04-30 | 2013-12-03 | Siegwerk Druckfarben Ag & Co. Kgaa | Photoinitiators |
| CN104497220A (en) * | 2015-01-04 | 2015-04-08 | 西南石油大学 | Starlike anti-shearing polyacrylamide for fracturing fluid and preparation method of starlike anti-shearing polyacrylamide |
| CN104558630A (en) * | 2015-01-04 | 2015-04-29 | 西南石油大学 | Water-soluble photoinitiator of thioxanthone-modified dendritic polyamide-amine and synthesis method |
| CN106933029A (en) * | 2015-12-31 | 2017-07-07 | 大东树脂化学股份有限公司 | Alkali-soluble smooth initiator copolymer of novelty tool as well as preparation method and application thereof |
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